Martin herzberg



UNITED STATES PATENT MARTIN IIERZBERG, AUGUST BLANK, AND ADOLF ISRAEL, OF ELBERFELD, GERMANY, ASSIGNORS TO THE FARBENFABRIKEN, VORMALS FR. BAYER d: (X), OF SAME PLACE.

B LACK AZO DYE.

SPECIFICATION forming part of Letters Patent No. 561,709, dated June 9, 1896.

Application filed November 8, 1895. Serial No. 568,349. (Specimens) Patented in England A ril 10, 1893, No. 7,330; in France May 2, 1893, No. 229,776, and in Austria-Hungary September 5,1893, No. 3,397 and No. 3,282.

To aZZ whom it may concern.- about twenty-four hours-viz., when the liq- Be it known that we, MARTIN HERZBERG, uid obtained by filtering a test portion of the AUGUST BLANK, and ADOLF ISRAEL, doctors reactionmixture and mixing the filtrate with of philosophy, chemists, assignors to the FAR- an alkaline solution of the so-called Schiif- 5 BENFABRIKEN, VORMALS FR. BAYER Lil? (30., of fers salt gives no longer a dyestuff. hen

Elberfeld, Prussia, Germany, residing at the this stage is arrived at, eighteen parts, by same place, have invented a new and useful weight,of metaphenylenediamin hydrochlorid Improvement in the Manufacture of Black dissolved in a sufficient quantity of Water, Azo Dyes, for which the aforesaid FARBEN- are added to the above acid mixture. After IO FABRIKEN, VORMALs FR. BAYER & Co. have standing and stirring Well for about twelve already obtained Letters Patent, as follows: hours the so-formed dyestuli is filtered 01f in France, No. 229,7 7 6, dated May 2, 1893 in and mixed again with cold water with the ad- England, No. 7,330, dated April 10, 1893, and dition of sixty kilos, by Weight, of sodium in Austria-Hungary, tom. as, fol. 3,397, tom. carbonate, (N21 00 Into this solution the i5 27, fol. 3,282, dated September 5, 1893;) and diazo compound, prepared by diazotizing fifwe do hereby declare the following to be an teen parts, by Weight,ofacetylparaphenyleneexact and clear description of our invention. diamin in the Well-known manner, is stirred.

()ur invention relates to the production of After about twelve hours the mixture is heatnew black azo dyes, which consists in first ed and the dyestuff is salted out by means 20 producing" the mixed dyestuffs from one 1110- of common salt and filtered off. It may be lccular proportion of the tetrazo compounds purified by redissolving in hot water and saltof paradiamins-such as benzidin, its analoing out. After filtering off, pressing, and gous and homologous bodies one molecudrying the dyestuii, which corresponds problar proportion of amidonaphthol disulfo-acid ably With the formula 5 (N11,: SO llzSO Hz Ol-I l. 3. 6. 8) or an alka- V line salt thereof, and one molecular propor- 6 7 5 tion of a metadiamin, such as metaphenylene- C H G H diamin or metatoluylendiamin, and in subsem SO Na quently allowing one molecular proportion of SO 0 diazotized acetylparaphenylenediamin to act on the aforesaid mixed dyestufis. The dye- NH stuffs thus obtained produce on unmordanted 4 T M cotton deep-black shades, fast to the action can L H \THCH C0 of alkali and acid. 6 3 35 In carrying out our invention practically forms a black powder, soluble in water with We can proceed as follows: 18% parts, by a black color, almost insoluble in alcohol, 8 5 Weight, of benzidin are converted in the Wellstrongsoda-lye, and strong sodiunrcarbonate known manner into the tetrazo compound by solution, soluble in ammonia liquor with a means of fifty-five parts, by Weight, of hyblack color. On adding dilute mineral acids 40 drochloric acid (20 Baum) and 13.8 parts, to the solution of the dyestuii in water a VlO- by weight, of sodium nitrite. The so-formed let-black precipitate is obtained. By con- 0 tetrazo solution is then stirred into a mixture contra-ted sulfuric acid (66 Baum) it is disprepared by mixing 34.1 parts, by Weight, of solved with a bluish-black color, a black prethe acid sodium salt of alnidonaphthol disulcipitate being formed when the above sulfo-acid (Nll z S0 11: SO lI: Oll l. 3. 0. S) in furic acid solution is mixed with a large three hundred and eighty parts, byweight, of quantity of ice water. The dyestuft produces 5 Water, the whole being well cooled down by on unmordanted cotton black shades of great means of ice. The formation of the resultresistance to the action of alkali and acid. ing intermediate product is complete after The same product is probably obtained if the intermediate product from one molecular proportion of tetrazotized benzidin and one molecular proportion of the aforesaid amidenaphtholdisulfo-acid (NH :SO H :SO H OH: 1 :3: G 8) is mixed in an acetic acid or alkaline solution with one molecular proportion of the chrysoidin-like product, which results from the combination of diazotized acetylparaphenylenediamin with metaphenylenediamin, and if the resulting mixture is finally alkalized with sodium carbonate, according to the directions given in the above example, the combination of the employed components can be efiected in alkaline as well as in acid solu tion. However, it must be pointed-out that the amidonaphtholdisulfo-acid is most practically coupled in a mineral acid solution,

, while acetylparaphenylenediamin (or another equivalent thereof) must always be coupled in the presence of an alkali.

Instead of benzidin any paradiamin may be substituted in molecular proportion in the above example, and instead of metaphenylenediamin hydrochlorid any other metadiamin may be employed.

lVhen, therefore, in this application we refer to benzidin, we mean thereby to include also all of its equivalentsnamely, compounds of a similar nature. When We refer to metaphenylenediamin, we mean also to include all other metadiamins which possess similar properties, and likewise the known metadioxy derivatives of the benzene series which yield dyestuffs of analogous properties. Of course we mean also to include the acetylnaphthylenediamin compound instead of acetylparaphenylenediamin. The dyestuffs obtained by such substitutions are all intended to be included in the present invention.

Having now described our invention and in what manner'the same is to be performed, what we claim as new, and desire to secure by Letters Patent, is

1. The process for the production of substantive black azo dyes, which consists in combining one molecular proportion of tetrazotized paradiamins, first with one molecu lar proportion of amidonaphthol disulfo-acid (N11 S0 11: S0 11: 011:1:3: 6: S), or an alkaline salt thereof, then with one molecular proportion of a metadiamin, such as metaphenylenediamin, and in finally coupling the soformed mixed azo dyestuffs with one molecular proportion of diazotized acetylparaphenylenediamin, in the manner hereinbefore described.

2. The process for the production of substantive black azo dyes, which consists in combining one molecular proportion of tetrazotized benzidin, first with one molecular proportion of amidonaphthol disulfo-acid (NI l SO H: SO H: OH:1: 3: 6 8), or an alkaline salt thereof, then with one molecular proportion of a metadiamin, such as metaphenylenediamin, and in finally coupling the so-formed mixed azo dyestufi with one molecular proportion of diazotized acetylparaphenylene diamin, in the manner herereinbefore described.

3. The new class of dyestuffs herein described, of which the following dyestuff is an example,

OH C H -N:N- 0 11 SO Na SO Na and which are black powders, soluble in water with a black color, dark flakes being precipitated when the watery solution is mixed with dilute mineral acids, almost insoluble in al cohol, strong soda-lye and sodium carbonate solution, being dissolved by concentrated sulfuric acid (66 Baum) with a bluish-black color, black flakes being precipitated on the addition of a large quantity of ice-water to the sulfuric-acid solution, producing on unmordanted cotton black shades of. great resistance to the action of alkali and acid.

In testimony where We have signed our names in the presence of two subscribing witnesses.

MARTIN HERZBERG. AUGUST BLANK. ADOLF ISRAEL. WVitnesses:

F. H. STRAUSS, A. STRAUSS. 

